The present invention relates to novel soluble chromophores containing carbamate groups, to their preparation and to the use thereof as fluorescent pigments and as pigment precursors which can be readily converted into the corresponding pigments.
N-substituted pyrrolo[3,4-c]pyrroles are disclosed in U.S. Pat. No. 4,585,878 and 4,791,204. From the generic definition of all substituents it can be inferred that the N-substituents may also be, inter alia, alkoxycarbonyl groups, which are defined in U.S. Pat. No. 4,791,204 as including methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, n-butoxycarbonyl and n-hexyloxycarbonyl. U.S. Pat. No. 4,585,878 teaches that the N-substituted pyrrolo[3,4-c]-pyrroles disclosed therein exhibit high fluorescence in dissolved form in polymers.
The invention provides novel carbamate group-containing soluble chromophores which, surprisingly, exhibit a very high solid state fluorescence, especially in the UV range, and which are readily convertible into the corresponding pigments with simultaneous displacement of the absorption spectrum, and hence open the way to unexpected applications.
Accordingly, the invention relates to compounds of formula
A(B)x,xe2x80x83xe2x80x83(I),
wherein x is an integer from 1 to 4,
A is the radical of a chromophore of the quinacridone, anthraquinone, perylene, indigo, quinophthalone, isoindolinone, isoindoline, dioxazine, phthalocyanine or azo series, which radical contains x N-atoms attached to B, preferably with at least one directly adjacent or conjugated carbonyl group,
B is a group of formula 
and, if x is 2, 3 or 4, may also be one, two or three hydrogen atoms, in which formulae (II), (III) and (IV)
m, n and p are each independently of one another 0 or 1,
X is C1-C14alkylene or C2-C8alkenylene,
Y is a group xe2x80x94Vxe2x80x94(CH2)qxe2x80x94,
Z is a group xe2x80x94Vxe2x80x94(CH2)rxe2x80x94,
V is C3-C6cycloalkylene,
q is an integer from 1 to 6, and
r is an integer from 0 to 6,
R1 and R2 are each independently of the other hydrogen, C1-C6alkyl, C1-C4alkoxy, halogen, CN, NO2, unsubstituted phenyl or phenoxy or phenyl or phenoxy which are substituted by C1-C4alkyl, C1-C4alkoxy or halogen,
Q is hydrogen, CN, Si(R1)3,
xe2x80x83is a group C(R5)(R6)(R7),
wherein R5, R6 and R7 are each independently of one another hydrogen or halogen and
xe2x80x83at least one of R5, R6 and R7 is halogen,
xe2x80x83a group 
wherein R1 and R2 are as defined above, a group SO2R8 or SR8, wherein R8 is C1-C4alkyl,
xe2x80x83is a group CH(R9)2, wherein R9 is unsubstituted phenyl or phenyl which is substituted by C1-C4alkyl, C1-C4alkoxy or halogen,
or
is a group of formula 
R3 and R4 are each independently of the other hydrogen, C1-C18alkyl, a group 
wherein X, Y, R1, R2, m and n are as defined above, or R3 and R4, together with the linking nitrogen atom, form a pyrrolidinyl, piperidinyl or morpholinyl radical.
A is the radical of a known chromophore having the basic structure
A(H)x,
for example 
and all known derivatives thereof.
X in the significance of C1-C14alkylene is straight-chain or branched alkylene, typically methylene, dimethylene, trimethylene, 1-methylmethylene, 1,1-methylmethylene, 1,1-dimethyldimethylene, 1,1-dimethyltrimethylene, 1-ethyldimethylene, 1-ethyl-1-methyldimethylene, tetramethylene, 1,1-dimethyltetramethylene, 2,2-dimethyltrimethylene, hexamethylene, decamethylene, 1,1-dimethyldecamethylene, 1,1-diethyldecamethylene or tetradecamethylene.
X in the significance of C1-C8alkenylene is straight-chain or branched alkenylene, typically vinylene, allylene, methallylene, 1-methyl-2-butenylene, 1,1-dimethyl-3-butenylene, 2-butenylene, 2-hexenylene, 3-hexenylene or 2-octenylene.
Halogen substituents may be iodo, fluoro, preferably bromo and, most preferably, chloro.
C1-C6Alkyl will typically be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-amyl, tert-amyl, hexyl, and C1-C18alkyl may additionally be heptyl, octyl, 2-ethylhexyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl.
C1-C4Alkoxy is typically methoxy, ethoxy, n-propoxy, isopropoxy or butoxy.
C3-C6Cycloalkylene is typically cyclopropylene, cyclopentylene and, preferably, cyclohexylene.
Particularly interesting compounds of formula I are those wherein x is 1 or 2 and B is a group of formula 
and, if x is 2, may also be one hydrogen atom, and in formulae IV, V and VI
m is 0 or 1,
X is C1-C4alkylene or C2-C5alkenylene,
R1 and R2 are each independently of the other hydrogen, C1-C4alkyl, methoxy, chloro or
NO2, and
Q is hydrogen, CN, CCl3, a group 
xe2x80x83SO2CH3 or SCH3,
R3 and R4 are each independently of the other hydrogen, C1-C4alkyl or a group 
or R3 and R4, taken together, form a piperidinyl radical,
and preferably those wherein x is 2 and B may be twice a group of formula 
Preferred compounds of formula I are
a) perylenecarboximides of formula 
wherein D is hydrogen, C1-C6alkyl, unsubstituted or halogen- or C1-C4alkyl-substituted phenyl, benzyl or phenethyl, or is B,
b) quinacridones of formula 
wherein R10 and R11 are each independently of the other hydrogen, halogen, C1-C18alkyl, C1-C4alkoxy or phenyl,
c) dioxazines of formula 
wherein R12 is hydrogen, halogen or C1-C18alkyl,
d) isoindolines of formulae 
wherein R13 is a group 
R14 is hydrogen, C1-C18alkyl, benzyl or a group 
R15 has the same meaning as R13,
R16, R17, R18 and R19 are each independently of one another hydrogen, C1-C18alkyl, C1-C4alkoxy, halogen or trifluoromethyl,
e) indigo derivatives of formula 
wherein R20 is hydrogen, CN, C1-C4alkyl, C1-C4alkoxy or halogen,
f) azobenzimidazolones of formula 
wherein R21 and R22 are each independently of the other hydrogen, halogen, C1-C4alkyl or C1-C4alkoxy,
g) anthraquinoid compounds of formula 
xe2x80x83and
h) phthalocyanines of formula 
xe2x80x83wherein
X1 is H2, Zn, Cu, Ni, Fe or V,
X2 is xe2x80x94CH(R24)xe2x80x94 or xe2x80x94SO2xe2x80x94
R23 is hydrogen, C1-C4alkyl, xe2x80x94N(E)R24, xe2x80x94NHCOR25, xe2x80x94COR25 or 
R24 is hydrogen or C1-C4alkyl, R25 is C1-C4alkyl and R26 is hydrogen, halogen, C1-C4alkyl or C1-C4alkoxy,
z is 0 or 1 and y is an integer from 1 to 4,
in each of which formulae E is hydrogen or is B, with the proviso that E in each formula is at least one group B and B is as defined above, in respect of which definition the preferred meanings cited above apply.
Among the phthalocyanines, those of formula XVI, wherein X1 is H2, Cu or Zn, X2 is xe2x80x94CH2xe2x80x94 or xe2x80x94SO2xe2x80x94, R23 is hydrogen, xe2x80x94NHCOCH3 or benzoyl and z is 1, are preferred.
In U.S. Pat. No. 4,585,878 it is said in connection with the preparation of N-unsubstituted pyrrolpyrroles that they can be obtained by reacting a N-substituted pyrrolo-3,4-c-pyrrole with a compound that carries the corresponding N-substituents as leaving groups in an organic solvent. In the sole Example describing a compound containing a N-carbonyl group (Example 9: N-benzoyl), 1,4-diketo-3,6-diphenyl-pyrrolo[3,4-c]pyrrole is reacted with benzoyl chloride. In the experiment to prepare the desired carbamates in analogous manner by reaction with a corresponding acid chloride derivative, it was unfortunately found that it was only possible to obtain said carbamates in poor yield.
Very surprisingly, however, it was observed that when using appropriate trihaloacetates, azides, carbonates, alkylidene-iminooxyformates or, in particular, appropriate dicarbonates, the desired carbamates are obtained in very good yield. An improved yield is also obtainedxe2x80x94even if only to a lesser degreexe2x80x94by carrying out the reaction with an aliphatic acid chloride derivative, conveniently butyl chloroformate, in the presence of a base as catalyst.
Accordingly, the invention further relates to a process for the preparation of compounds of formula I, which comprises reacting a compound of formula
A(H)x,xe2x80x83xe2x80x83(XVII)
wherein A and x are as defined above, in the desired molar ratio with a dicarbonate of formula
Bxe2x80x94Oxe2x80x94Bxe2x80x83xe2x80x83(XVIII)
or with a trihaloacetate of formula
xe2x80x83(R27)3Cxe2x80x94Bxe2x80x83xe2x80x83(XIX),
or with an azide of formula
BN3xe2x80x83xe2x80x83(XX),
or with a carbonate of formula
Bxe2x80x94OR28xe2x80x83xe2x80x83(XXI),
or with an alkylidene-iminooxyformate of formula 
wherein B is as defined above, R27 is chloro, fluoro or bromo, R28 is C1-C4alkyl or unsubstituted phenyl or phenyl which is substituted by halogen, C1-C4alkyl, C1-C4alkoxy or xe2x80x94CN, R29 is xe2x80x94CN or xe2x80x94COOR18, and R30 is unsubstituted phenyl or phenyl which is substituted by halogen, C1-C4alkyl, C1-C4alkoxy or xe2x80x94CN, in an aprotic organic solvent and in the presence of a base as catalyst, conveniently in the temperature range from 0 to 400xc2x0 C., preferably from 10 to 200xc2x0 C., for 2 to 80 hours.
It is preferred to react the compound of formula XVII with a dicarbonate of formula XVIII.
The compounds of formula XVII, dicarbonates of formula XVIII, trihaloacetates of formula XIX, azides of formulae XX, carbonates of formula XXI and alkylidene-iminooxyformates of formula XXII are known substances. Any that are novel can be prepared by methods analogous to standard known ones.
The respective molar ratio of the compound of formula XVII and the compounds of formulae XVIII-XXII will depend on the meaning of x, i.e. on the number of groups B to be introduced. Preferably, however, the compounds of formulae XVIII-XXII will be used in a 2- to 10-fold excess.
Suitable solvents are typically ethers such as tetrahydrofuran or dioxane, or glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether, and also dipolar aprotic solvents such as acetonitrile, benzonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, nitrobenzene, N-methylpyrrolidone, halogenated aliphatic or aromatic hydrocarbons such as trichloroethane, benzene or alkyl-, alkoxy- or halogen-substituted benzene, typically including toluene, xylene, anisole or chlorobenzene, or aromatic N-heterocycles such as pyridine, picoline or quinoline. Preferred solvents are typically tetrahydrofuran, N,N-dimethylformamide and N-methylpyrrolidone. The cited solvents may also be used as mixtures. It is convenient to use 5-20 parts by weight of solvent to 1 part by weight of reactant.
Bases suitable as catalysts are typically the alkali metals themselves, conveniently lithium, sodium or potassium and the hydroxides or carbonates thereof, or alkali metal amides such as lithium, sodium or potassium amide or alkali metal hydrides such as lithium, sodium or potassium hydride, or alkaline earth metal or alkali metal alcoholates which are derived in particular from primary, secondary or tertiary aliphatic alcohols of 1 to 10 carbon atoms, for example lithium, sodium or potassium methylate, ethylate, n-propylate, isopropylate, n-butylate, sec-butylate, tert-butylate, 2-methyl-2-butylate, 2-methyl-2-pentylate, 3-methyl-3-pentylate, 3-ethyl-3-pentylate, and also organic aliphatic aromatic or heterocyclic N-bases, typically including diazabicyclooctene, diazabicycloundecene and 4-dimethylaminopyridine and trialkylamines such as trimethylamine or triethylamine. A mixture of the cited bases may also be used.
The organic nitrogen bases are preferred, for example diazabicyclooctene, diazabicycloundecene and preferably, 4-dimethylaminopyridine.
The reaction is preferably carried out in the temperature range from 10 to 100xc2x0 C., most preferably from 14 to 40xc2x0 C., and under atmospheric pressure.
The novel compounds of formula I are admirably suitable for use as fluorescent pigments for the mass colouration of organic material of high molecular weight.
Illustrative examples of high molecular weight organic materials which can be coloured with the novel compounds of formula I are vinyl polymers such as polystyrene, poly-xcex1-methylstyrene, poly-p-methylstyrene, poly-p-hydroxystyrene, poly-p-hydroxyphenylstyrene, poly(methylacrylate) and poly(acrylamide) as well as the corresponding methacrylic compounds, poly(methylmaleate), poly(acrylonitrile), poly(methacrylonitile), poly(vinyl chloride), poly(vinyl fluoride), poly(vinylidene chloride), poly(vinylidene fluoride), poly(vinyl acetate), poly(methyl vinyl ether) and poly(butyl vinyl ether); novolaks derived from C1-C6aldehydes, typically formaldehyde and acetaldehyde, and a binuclear, preferably mononuclear, phenol which may be substituted by one or two C1-C9alkyl groups, one or two halogen atoms or a phenyl ring, for example o-, m- or p-cresol, xylene, p-tert-butyl phenol, o-, m- or p-nonylphenol, p-chlorophenol or p-phenylphenol, or from a compound containing more than one phenolic group, e.g. resorcinol, bis(4-hydroxyphenyl)methane or 2,2-bis(4-hydroxyphenyl)propane; polymers derived from maleimide and/or maleic anhydride, e.g. copolymers of maleic anhydride and styrene; poly(vinylpyrrolidone), biopolymers and derivatives thereof such as cellulose, starch, chitine, chitosane, gelatin, zein, ethyl cellulose, nitrocellulose, cellulose acetate and cellulose butyrate; natural resins and synthetic resins such as rubber, casein, silicone and silicone resins, ABS, urea/formaldehyde and melamine/formaldehyde resins, alkyd resins, phenolic resins, polyamides, polyimides, polyamide/imides, polysulfones, polyether sulfones, polyphenylene oxides, polyurethanes, polyureas, polycarbonates, polyarylenes, polyarylene sulfides, polyepoxides, polyolefins and polyalkadienes. Preferred high molecular weight organic materials are typically cellulose ethers and esters, for example ethyl cellulose, nitrocellulose, cellulose acetate or cellulose butyrate, natural resins or synthetic resins such as polymerisation or condensation resins, for example aminoplasts, in particular urea/formaldehyde and melamine/formaldehyde resins, alkyd resins, phenolic plastics, polycarbonates, polyolefins, polystyrene, polyvinyl chloride, polyamides, polyurethanes, polyesters, ABS, polyphenylene oxide, rubber, casein, silicone and silicone resins, singly or in mixtures.
The above high molecular weight organic compounds may be singly or as mixtures in the form of plastic materials, melts or of spinning solutions, paint systems, coating materials or printing inks. Depending on the end use requirement, it is expedient to use the novel compounds of formula I as toners or in the form of preparations.
The novel compounds of formula I are particularly suitable for the mass coloration of polyesters, polyvinyl chloride and, preferably, polyolefins such as polyethylene and polypropylene, as well as paint systems, also powder coating compositions, printing inks and coating materials.
The novel compounds of formula I can be used in an amount of 0.01 to 30% by weight, preferably 0.1 to 10% by weight, based on the high molecular weight organic material to be pigmented.
The pigmenting of the high molecular weight organic materials with the novel compounds of formula I is conveniently effected by incorporating a compound of formula I by itself or in the form of a masterbatch in the substrates using roll mills, mixing or miling apparatus. The pigmented material is then brought into the desired final form by methods which are known per se, conveniently by calendering, moulding, extruding, coating, casting or by injection moulding. It is often desirable to incorporate plasticisers into the high molecular weight compounds before processing in order to produce non-brittle mouldings or to diminish their brittleness. Suitable plasticisers are typically esters of phosphoric acid, phthalic acid or sebacic acid. The plasticisers may be incorporated before or after blending the pigment salts of this invention into the polymers. To obtain different shades it is also possible to add fillers or other chromophoric components such as white, coloured or black pigments in any amount to the high molecular weight organic materials in addition to the novel compounds of this invention.
For pigmenting paint systems, coating materials and printing inks, the high molecular weight organic materials and the novel compounds of formula I, together with optional additives such as fillers, other pigments, siccatives or plasticisers, are finely dispersed or dissolved in a common organic solvent or mixture of solvents. The procedure may be such that the individual components by themselves, or also several components together, are dispersed or dissolved in the solvent and thereafter all the components are mixed.
When used for colouring, inter alia, polyvinyl chloride or polyolefins or printing inks, the novel compounds of formula I have good allround pigment properties, including good fastness to migration, light and weathering, and especially unexpectedly high fluorescence.
Of very great importance, however, is the entirely unexpected ease with which the soluble chromophores of this inventionxe2x80x94even in the substrate in which they have already been incorporatedxe2x80x94can be converted to the corresponding chromophore of formula A(H)x. This can be done in the simplest manner, whether by thermal treatment (heating to the temperature range from 50 to 400xc2x0 C., preferably from 100 to 200xc2x0 C. or laser radiation), photolytic treatment (exposure to wavelengths below e.g. 375 nm) or chemical treatment (with organic or inorganic acids or bases) of the solid materials, solutions or dispersions containing the novel chromophores in organic or aqueous media, polymer solutions or melts. These conversion methods can also be combined, thereby permitting the coloration of paint systems, printing inks, especially for ink jet printing, and plastics, also in fibre form, with unexpectedly enhanced properties such as purity, colour strength, brilliance and transparency, as well as interesting applications in the analytical field.
It has even been found that the chemical treatment of specific chromophores of formula I with an organic or inorganic acid at 50 to 180xc2x0 C., preferably from 80 to 160xc2x0 C., and subsequent cooling to about 70 to 100xc2x0 C., or the thermal treatment of said compounds by heating to the temperature range from 180-350xc2x0 C., can result in crystal modifications of the corresponding chromophores of formula XVII.
The invention therefore additionally relates to a process for the crystal modification of chromophores of formula XVII, comprising
a) the chemical treatment of a chromophore of formula I with an organic or inorganic acid at 50 to 180xc2x0 C. and subsequent cooling,
or
b) the thermal treatment of a chromophore of formula I in the temperature range from 180 to 350xc2x0 C.